CA1228316A - Treating residua with layers of differently impregnated hydroprocessing catalysts - Google Patents
Treating residua with layers of differently impregnated hydroprocessing catalystsInfo
- Publication number
- CA1228316A CA1228316A CA000437430A CA437430A CA1228316A CA 1228316 A CA1228316 A CA 1228316A CA 000437430 A CA000437430 A CA 000437430A CA 437430 A CA437430 A CA 437430A CA 1228316 A CA1228316 A CA 1228316A
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- Prior art keywords
- catalyst
- weight percent
- metal
- group viii
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method for hydrotreating heavy hydrocarbon-Swiss feed stocks containing high levels of contaminant metals, nickel, iron, and vanadium, and contaminant sulfur. The feed is contacted under hydroprocessing conditions with at least two catalysts that are made by impregnating the same support with different levels of catalytic metals. The first catalyst contacted has no more than 4 weight percent Group VIII metals and no more than 8 weight percent Group VI metals, and the second catalyst has at least 2 weight percent Group VIII metals and at least 3 weight percent Group VI metals.
A method for hydrotreating heavy hydrocarbon-Swiss feed stocks containing high levels of contaminant metals, nickel, iron, and vanadium, and contaminant sulfur. The feed is contacted under hydroprocessing conditions with at least two catalysts that are made by impregnating the same support with different levels of catalytic metals. The first catalyst contacted has no more than 4 weight percent Group VIII metals and no more than 8 weight percent Group VI metals, and the second catalyst has at least 2 weight percent Group VIII metals and at least 3 weight percent Group VI metals.
Description
SLY
TREATING RESIDUE WITH LAYERS OF DIFFERENTLY
IMPREGNATED HYDROPROCESSING CATALYSTS
This invention relates to methods of hydropower-cussing metals contaminated hydrocarbonaceous feed stocks.
In particular this invention relates to hydrodemetallation of metals contaminated petroleum feed stocks.
Refiners must refine heavier, more contaminated feed stocks as the world's supply of petroleum diminishes.
Metals contained in the feed stock must be removed for several reasons. During refining, metals tend to prom-surely deactivate catalysts by depositing in layers, 15 thereby eventually blocking the catalysts pores. Metals can cause corrosion problems during transit and combs-lion, and the exhaust gases from such combustion have adverse environmental impact.
A variety of schemes to remove metals have been tried. The simplistic approach of frequently changing a hydrodesulfurization catalyst works, but is wasteful since the spent catalyst tends not to be fully utilized. More complicated schemes of layering varieties of catalysts that differ in pore size, support composition, and metals 25 loadings can give more efficient use of the individual catalysts. However, this general method requires several different catalysts that must frequently be manufactured by very different techniques. Most layering schemes involve contacting the-feedstock with a catalyst having 30 large pores designed more for metal capacity before deco-tivation by pore blockage, and then catalysts with smaller pores and generally more catalytic metals to remove nest-dual metals and sulfur.
SUMMARY OF THE INVENTION
A method is provided for hydroprocessing hydra-carbonaceous feed stocks comprising:
contacting the feed stock with hydrogen under hydra-processing conditions, in a first catalyst zone, contain-in a first catalyst characterized by having no more than 40 4 weight percent Group VIII metal and no more than n, ' .
~228316 8 weight percent Group VI metal, thereby producing an effluent; and 05 contacting the effluent with hydrogen under hydropower-cussing conditions, in a second catalyst zone, containing a second catalyst characterized by having at least
TREATING RESIDUE WITH LAYERS OF DIFFERENTLY
IMPREGNATED HYDROPROCESSING CATALYSTS
This invention relates to methods of hydropower-cussing metals contaminated hydrocarbonaceous feed stocks.
In particular this invention relates to hydrodemetallation of metals contaminated petroleum feed stocks.
Refiners must refine heavier, more contaminated feed stocks as the world's supply of petroleum diminishes.
Metals contained in the feed stock must be removed for several reasons. During refining, metals tend to prom-surely deactivate catalysts by depositing in layers, 15 thereby eventually blocking the catalysts pores. Metals can cause corrosion problems during transit and combs-lion, and the exhaust gases from such combustion have adverse environmental impact.
A variety of schemes to remove metals have been tried. The simplistic approach of frequently changing a hydrodesulfurization catalyst works, but is wasteful since the spent catalyst tends not to be fully utilized. More complicated schemes of layering varieties of catalysts that differ in pore size, support composition, and metals 25 loadings can give more efficient use of the individual catalysts. However, this general method requires several different catalysts that must frequently be manufactured by very different techniques. Most layering schemes involve contacting the-feedstock with a catalyst having 30 large pores designed more for metal capacity before deco-tivation by pore blockage, and then catalysts with smaller pores and generally more catalytic metals to remove nest-dual metals and sulfur.
SUMMARY OF THE INVENTION
A method is provided for hydroprocessing hydra-carbonaceous feed stocks comprising:
contacting the feed stock with hydrogen under hydra-processing conditions, in a first catalyst zone, contain-in a first catalyst characterized by having no more than 40 4 weight percent Group VIII metal and no more than n, ' .
~228316 8 weight percent Group VI metal, thereby producing an effluent; and 05 contacting the effluent with hydrogen under hydropower-cussing conditions, in a second catalyst zone, containing a second catalyst characterized by having at least
2 weight percent Group VIII metal and at least 3 weight percent Group VI metal The first and second catalysts are the same support impregnated with different amounts of catalytic metals.
DETAILED DESCRIPTION
It has been discovered that passing a feed stock 1 that contains contaminant metals through layered catalyst beds containing catalysts with the same support that have progressively increasing levels of catalytic metals, removes the contaminant metals and provides a system with long catalyst life.
FEED STOCKS
The feed stocks of this invention can be any hydrocarbonaceous feed stocks that contain sulfur and con-taminant metals. Contaminant metals are those metals which are dissolved in the feed and include nickel, vane-drum and iron.
The feed stocks of this invention will be those having more than 20 Pam No + Fe + V, herein defined as contaminant metals and preferably those having more than 50 Pam contaminant metals. These feed stocks will typically also contain more than 1 weight percent sulfur and frequently more than 3 weight percent. These stocks can be crudest topped crudest atmospheric or vacuum residue, and liquids from synthetic feed processes, such as liquids from coal or oil shale.
CATALYSTS
The catalysts of this invention can be any hydroprocessing catalyst supported on refractory inorganic oxides. The support can include alumina, silica, magnet slum, titanic and the like as well as mixtures, such as silica-alumina and the like. Naturally occurring clays 12283~6 can also be used. For example, the fibrous clays, await-pulgite and sepiolite, magnesium silicate clays, and US hollowest, an aluminum silicate clay, all defined herein as "fibrous clays", are excellently suited for this invention.
The catalysts of this invention are typically made by manufacturing a support and then impregnating the lo support with the catalytically active metals. Therefore, the final catalysts tend to have the pore characteristics of the support material. The pore size and distribution can be slightly affected by impregnation. For the pun-poses of this invention, if impregnation effect is less lo than 10% difference in calculated geometric pore diameter, it can be ignored. It is preferred that the support have pores large enough for effective demetallation. Effective demetallation and residuum catalysts frequently have more than 50% of the pore volume contributed by pores larger MU than loo and will preferably have an average microspore diameter of between AYE and AYE. Geometric pore size is the result of the calculation 40000 x PI = APT
SPA
where PI is pore volume and SPA is surface area. APT is average pore diameter and is based on the approximation that the pores are circular in cross-section. Up to 50%
of the total pore volume can be contributed by macro pores, defined herein as pores larger than Lowe calculated die-meter, and frequently 10% of the total pore volume will be contributed by macro pores. If fibrous clays are used as support material, the geometric pore size frequently ranges between AYE and AYE with very little of the total pore volume contributed by pores smaller than AYE.
Relatively large pores are preferred because contaminant metals tend to deposit onto the catalyst sun-face, which, in time, plugs the pores, and demetallation and desulfurization are diffusion limited reactions.
- ~,Zz83~6 Larger pores facilitate the diffusion of heavy viscous residue into the interior of the catalyst.
05 A support with the appropriate pore size disk tribution can then be impregnated with catalytic metals.
In general, several different catalytic metals loading levels will be impregnated onto the same support, result-in in several catalysts of varying activity.
Catalytic metals can be metals from Group VIII
of the Periodic Table or Group VI. In particular, cobalt and nickel are preferred Group VIII metals, and molybdenum and tungsten are preferred Group VI metals. These metals can be used singly or in combination, for example, cobalt-molybdenum, cobalt-tungsten or nickel-molybdenum.
For the operation of this invention at least two different catalysts must be used that preferably vary in their pore size and pore size distribution characteristics by no more than 10%. It is preferable that one catalyst contain low levels of only one catalytic metal, while the other catalyst contains a combination of catalytic metals.
The first catalyst of this invention will be characterized by having no more than 4 weight percent of a Group VIII metal and no more than 8 weight percent of a Group VI metal impregnated onto the support, and the second catalyst will be characterized by having at least 2 weight percent Group VIII metal, preferably at least 5 weight percent Group VIII metal, and at least 3 weight percent of a Group VI metal and preferably at least 8 weight percent of Group III metal.
It may be desirable to contact a given feed with more than two catalyst beds. For example, the feed stock may be contacted with three catalysts. The first catalyst will contain no more than 5 weight percent Group VIII
metal, the second no more than 4 weight percent Group VIII
metal and no more than 7 weight percent Group VI metal.
The third catalyst will contain at least 3 weight percent Group VIII metal and at least 8 weight percent Group VI
metal. In such a scheme the first catalyst produces a first effluent stream which contacts the second catalyst, ~L2Z83~6 producing in turn a second effluent stream which contacts the third catalyst, which produces the product.
LAYERING
In the process of this invention the catalyst will be layered so that the feed stock to be hydroprocessed will contact hydrogen in the presence of a series of more active hydroprocessing catalysts. The catalysts are pro-ferentially graded with respect to activity so that each layer of catalyst shows approximately the same disturb-lion factor when the spent particles from that bed are examined by electron probes. The "distribution factor" is defined as average metal level/maximum metal level, and I can be measured by the amount of metals, typically nickel and vanadium, deposited as a function of radius in the cross-section of a spent catalyst particle. The disturb-lion factor does not assume that the maximum level of metal deposition is always at the outer edge. With a feed I that contains contaminant metals, it would be ideal if all the catalyst particles in the reactor have essentially the same distribution factors. Therefore, no portion of the catalyst in the reactor would be deactivated by metals deposition earlier than any other portion of the catalyst, thereby maximizing the total life of the catalyst charge in the reactor The more contaminated feed contacts less active catalyst, thereby allowing the feed to penetrate the catalyst more fully before metal deposition occurs.
As the feed becomes less contaminated, it contacts more active catalysts that promote the deposition of more tightly bound metals and desulfurization. For any given feed stock there will be an ideal layering of catalysts that will result in the least variance of distribution factor from the top of the reactor to the bottom. The different catalysts of this invention are physically nearly identical, except for metals loading, making it easy to provide a bed of intermediate activity catalyst by the actual physical mixing of two catalysts, one of higher, the other of lower activity.
lZ283116 Examples Preparation of Support 05 A support useful in the present invention is prepared according to the procedure described in US.
Patent No 4,113,661 issued to P. W. Tam, September 12, 1978, entitled, "Method for Preparing a ~ydrodesulfuriza-lion Catalyst". An 80/20 by weight mixture of Catapal*, made by Kink, alumina and Kaiser alumina are sized in the range below about 150 microns and treated by thoroughly admixing the mixed powders with an aqueous solution of nitric acid, where for each formula weight of the alumina (AYE) about 0.1 equivalent of acid is used. The treated alumina powder is in the form of a workable paste. A sample of this paste completely disperses when one part is slurries in four parts by weight of water. The pi of the slurry is in the range of about 3.8 to about 4.2, usually about 4Ø After aqueous acid treatment of the powders, aqueous ammonium hydroxide is thoroughly admixed into the paste in an amount equivalent to about 80% of the ammonium hydroxide theoretically required to completely neutralize the nitric acid; that is, about 0.08 equivalent of the hydroxide is added to the paste per formula weight of the alumina present The ammonium hydroxide used is desirably about an 11~ by weight solution because the volatile material evolved during drying and calcination content of the treated and neutralized solids should be in the range of 50-70 weight percent. With the addition and thorough admixing of ammonium hydroxide, the paste changes to a free-flowing particulate solid suitable as a feed to an extrude. The extrude has a die plate that will extrude the shaped particles of the present invention. The extra-date precursor is freed of loosely-held water by an initial moderate drying step, for example, at a temperature in the range of 150F-500F. The preparation of the carrier is then completed by calcining the dried extradite at a temperature between 500F-1700F in a dry or humid atmosphere. The resulting carrier has a pore *Trade mark lZ2~33~6 volume of about 0.7 cc per gram, of which at least about 85% is furnished by pores having a diameter in the range US between about 80 and AYE. Less than about 1.0% of pore volume is furnished by pores larger than Lowe.
Catalyst A
Catalyst A was made by impregnating the support so obtained with enough cobalt carbonate and phosphomolyb-0 die acid in aqueous solution to give 2.5 weight percent cobalt, when weight percent is based on the reduced metal, and 11 weight percent molybdenum.
Catalyst B
Catalyst B was made by impregnating the support with enough cobalt carbonate and phosphomolybdic acid in aqueous solution to give 1.5 weight percent cobalt and 6 weight percent molybdenum.
Layering An Arabian Heavy Atmospheric Residuum, boiling at 730+ and having 4.6 weight percent sulfur, 28 Pam No and 90 Pam V, was treated according to the present invention. The first catalyst bed contained the catalyst described as catalyst B, and filled one-third of the reactor volume. The second catalyst bed contained the catalyst described as catalyst A and filled two-thirds of the reactor volume. The feed flowed through the reactor at 0.35 ho 1 space velocity, the hydrogen pressure was about 1800 psi, 5000 standard cubic football once through gas. The temperature was varied through the run to maintain about 0.6 percent sulfur, about 10 Pam No and between 25 Pam and 35 Pam V in the product. When the temperature reached 800F, the temperature limit of the vessel, the experiment was stopped. This limit was reached after 3700 hours of continuous operation.
When the same feed stock was contacted with a reactor filled with catalyst A, the temperature limit was reached after 2900 hours. The shapes of the catalysts used in the two tests were not identical. The shapes in the second catalyst test were extruded trilobal, whereas the shape in the first catalyst test was cylindrical. It was estimated that about one-third of the improved life was due to the layering, or about 10-12% improvement with 05 layering-I
DETAILED DESCRIPTION
It has been discovered that passing a feed stock 1 that contains contaminant metals through layered catalyst beds containing catalysts with the same support that have progressively increasing levels of catalytic metals, removes the contaminant metals and provides a system with long catalyst life.
FEED STOCKS
The feed stocks of this invention can be any hydrocarbonaceous feed stocks that contain sulfur and con-taminant metals. Contaminant metals are those metals which are dissolved in the feed and include nickel, vane-drum and iron.
The feed stocks of this invention will be those having more than 20 Pam No + Fe + V, herein defined as contaminant metals and preferably those having more than 50 Pam contaminant metals. These feed stocks will typically also contain more than 1 weight percent sulfur and frequently more than 3 weight percent. These stocks can be crudest topped crudest atmospheric or vacuum residue, and liquids from synthetic feed processes, such as liquids from coal or oil shale.
CATALYSTS
The catalysts of this invention can be any hydroprocessing catalyst supported on refractory inorganic oxides. The support can include alumina, silica, magnet slum, titanic and the like as well as mixtures, such as silica-alumina and the like. Naturally occurring clays 12283~6 can also be used. For example, the fibrous clays, await-pulgite and sepiolite, magnesium silicate clays, and US hollowest, an aluminum silicate clay, all defined herein as "fibrous clays", are excellently suited for this invention.
The catalysts of this invention are typically made by manufacturing a support and then impregnating the lo support with the catalytically active metals. Therefore, the final catalysts tend to have the pore characteristics of the support material. The pore size and distribution can be slightly affected by impregnation. For the pun-poses of this invention, if impregnation effect is less lo than 10% difference in calculated geometric pore diameter, it can be ignored. It is preferred that the support have pores large enough for effective demetallation. Effective demetallation and residuum catalysts frequently have more than 50% of the pore volume contributed by pores larger MU than loo and will preferably have an average microspore diameter of between AYE and AYE. Geometric pore size is the result of the calculation 40000 x PI = APT
SPA
where PI is pore volume and SPA is surface area. APT is average pore diameter and is based on the approximation that the pores are circular in cross-section. Up to 50%
of the total pore volume can be contributed by macro pores, defined herein as pores larger than Lowe calculated die-meter, and frequently 10% of the total pore volume will be contributed by macro pores. If fibrous clays are used as support material, the geometric pore size frequently ranges between AYE and AYE with very little of the total pore volume contributed by pores smaller than AYE.
Relatively large pores are preferred because contaminant metals tend to deposit onto the catalyst sun-face, which, in time, plugs the pores, and demetallation and desulfurization are diffusion limited reactions.
- ~,Zz83~6 Larger pores facilitate the diffusion of heavy viscous residue into the interior of the catalyst.
05 A support with the appropriate pore size disk tribution can then be impregnated with catalytic metals.
In general, several different catalytic metals loading levels will be impregnated onto the same support, result-in in several catalysts of varying activity.
Catalytic metals can be metals from Group VIII
of the Periodic Table or Group VI. In particular, cobalt and nickel are preferred Group VIII metals, and molybdenum and tungsten are preferred Group VI metals. These metals can be used singly or in combination, for example, cobalt-molybdenum, cobalt-tungsten or nickel-molybdenum.
For the operation of this invention at least two different catalysts must be used that preferably vary in their pore size and pore size distribution characteristics by no more than 10%. It is preferable that one catalyst contain low levels of only one catalytic metal, while the other catalyst contains a combination of catalytic metals.
The first catalyst of this invention will be characterized by having no more than 4 weight percent of a Group VIII metal and no more than 8 weight percent of a Group VI metal impregnated onto the support, and the second catalyst will be characterized by having at least 2 weight percent Group VIII metal, preferably at least 5 weight percent Group VIII metal, and at least 3 weight percent of a Group VI metal and preferably at least 8 weight percent of Group III metal.
It may be desirable to contact a given feed with more than two catalyst beds. For example, the feed stock may be contacted with three catalysts. The first catalyst will contain no more than 5 weight percent Group VIII
metal, the second no more than 4 weight percent Group VIII
metal and no more than 7 weight percent Group VI metal.
The third catalyst will contain at least 3 weight percent Group VIII metal and at least 8 weight percent Group VI
metal. In such a scheme the first catalyst produces a first effluent stream which contacts the second catalyst, ~L2Z83~6 producing in turn a second effluent stream which contacts the third catalyst, which produces the product.
LAYERING
In the process of this invention the catalyst will be layered so that the feed stock to be hydroprocessed will contact hydrogen in the presence of a series of more active hydroprocessing catalysts. The catalysts are pro-ferentially graded with respect to activity so that each layer of catalyst shows approximately the same disturb-lion factor when the spent particles from that bed are examined by electron probes. The "distribution factor" is defined as average metal level/maximum metal level, and I can be measured by the amount of metals, typically nickel and vanadium, deposited as a function of radius in the cross-section of a spent catalyst particle. The disturb-lion factor does not assume that the maximum level of metal deposition is always at the outer edge. With a feed I that contains contaminant metals, it would be ideal if all the catalyst particles in the reactor have essentially the same distribution factors. Therefore, no portion of the catalyst in the reactor would be deactivated by metals deposition earlier than any other portion of the catalyst, thereby maximizing the total life of the catalyst charge in the reactor The more contaminated feed contacts less active catalyst, thereby allowing the feed to penetrate the catalyst more fully before metal deposition occurs.
As the feed becomes less contaminated, it contacts more active catalysts that promote the deposition of more tightly bound metals and desulfurization. For any given feed stock there will be an ideal layering of catalysts that will result in the least variance of distribution factor from the top of the reactor to the bottom. The different catalysts of this invention are physically nearly identical, except for metals loading, making it easy to provide a bed of intermediate activity catalyst by the actual physical mixing of two catalysts, one of higher, the other of lower activity.
lZ283116 Examples Preparation of Support 05 A support useful in the present invention is prepared according to the procedure described in US.
Patent No 4,113,661 issued to P. W. Tam, September 12, 1978, entitled, "Method for Preparing a ~ydrodesulfuriza-lion Catalyst". An 80/20 by weight mixture of Catapal*, made by Kink, alumina and Kaiser alumina are sized in the range below about 150 microns and treated by thoroughly admixing the mixed powders with an aqueous solution of nitric acid, where for each formula weight of the alumina (AYE) about 0.1 equivalent of acid is used. The treated alumina powder is in the form of a workable paste. A sample of this paste completely disperses when one part is slurries in four parts by weight of water. The pi of the slurry is in the range of about 3.8 to about 4.2, usually about 4Ø After aqueous acid treatment of the powders, aqueous ammonium hydroxide is thoroughly admixed into the paste in an amount equivalent to about 80% of the ammonium hydroxide theoretically required to completely neutralize the nitric acid; that is, about 0.08 equivalent of the hydroxide is added to the paste per formula weight of the alumina present The ammonium hydroxide used is desirably about an 11~ by weight solution because the volatile material evolved during drying and calcination content of the treated and neutralized solids should be in the range of 50-70 weight percent. With the addition and thorough admixing of ammonium hydroxide, the paste changes to a free-flowing particulate solid suitable as a feed to an extrude. The extrude has a die plate that will extrude the shaped particles of the present invention. The extra-date precursor is freed of loosely-held water by an initial moderate drying step, for example, at a temperature in the range of 150F-500F. The preparation of the carrier is then completed by calcining the dried extradite at a temperature between 500F-1700F in a dry or humid atmosphere. The resulting carrier has a pore *Trade mark lZ2~33~6 volume of about 0.7 cc per gram, of which at least about 85% is furnished by pores having a diameter in the range US between about 80 and AYE. Less than about 1.0% of pore volume is furnished by pores larger than Lowe.
Catalyst A
Catalyst A was made by impregnating the support so obtained with enough cobalt carbonate and phosphomolyb-0 die acid in aqueous solution to give 2.5 weight percent cobalt, when weight percent is based on the reduced metal, and 11 weight percent molybdenum.
Catalyst B
Catalyst B was made by impregnating the support with enough cobalt carbonate and phosphomolybdic acid in aqueous solution to give 1.5 weight percent cobalt and 6 weight percent molybdenum.
Layering An Arabian Heavy Atmospheric Residuum, boiling at 730+ and having 4.6 weight percent sulfur, 28 Pam No and 90 Pam V, was treated according to the present invention. The first catalyst bed contained the catalyst described as catalyst B, and filled one-third of the reactor volume. The second catalyst bed contained the catalyst described as catalyst A and filled two-thirds of the reactor volume. The feed flowed through the reactor at 0.35 ho 1 space velocity, the hydrogen pressure was about 1800 psi, 5000 standard cubic football once through gas. The temperature was varied through the run to maintain about 0.6 percent sulfur, about 10 Pam No and between 25 Pam and 35 Pam V in the product. When the temperature reached 800F, the temperature limit of the vessel, the experiment was stopped. This limit was reached after 3700 hours of continuous operation.
When the same feed stock was contacted with a reactor filled with catalyst A, the temperature limit was reached after 2900 hours. The shapes of the catalysts used in the two tests were not identical. The shapes in the second catalyst test were extruded trilobal, whereas the shape in the first catalyst test was cylindrical. It was estimated that about one-third of the improved life was due to the layering, or about 10-12% improvement with 05 layering-I
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for hydroprocessing hydrocarbonaceous feedstocks comprising:
contacting said feedstock with hydrogen under hydro-processing conditions, in a first catalyst zone, contain-ing a first catalyst characterized by having no more than 4 weight percent Group VIII metal and no more than 8 weight percent Group VI metal, thereby producing an effluent; and contacting said effluent with hydrogen under hydro-processing conditions in a second catalyst zone, contain-ing a second catalyst, characterized by having at least 2 weight percent Group VIII metal and at least 3 weight percent Group VI metal.
contacting said feedstock with hydrogen under hydro-processing conditions, in a first catalyst zone, contain-ing a first catalyst characterized by having no more than 4 weight percent Group VIII metal and no more than 8 weight percent Group VI metal, thereby producing an effluent; and contacting said effluent with hydrogen under hydro-processing conditions in a second catalyst zone, contain-ing a second catalyst, characterized by having at least 2 weight percent Group VIII metal and at least 3 weight percent Group VI metal.
2. The process of Claim 1 wherein said feedstock contains at least 20 ppm V + Ni + Fe and at least 1.0 weight percent sulfur.
3. The process of Claim 1 wherein said first cata-lyst and said second catalyst are characterized by having more than 10% pore volume contributed by pores larger than 1000.ANG..
4. The process of Claim 1 wherein said first cata-lyst and said second catalyst are supported on alumina.
5. The process of Claim 4 wherein said first cata-lyst is made by impregnating the alumina support with no more than 4 weight percent Group VIII metal and no more than 8 weight percent Group VI metal, and said second catalyst is made by impregnating said alumina support with at least 2 weight percent Group VIII metal and at least 3 weight percent Group VI metal.
6. The process of Claim 1 wherein said first cata-lyst has different Group VIII metals than said second catalyst.
7. The process of Claim 1 wherein said Group VIII
metals include nickel and cobalt and said Group VI metals include molybdenum and tungsten.
metals include nickel and cobalt and said Group VI metals include molybdenum and tungsten.
8. The process of Claim 1 wherein said first and said second catalysts have more than 50 percent of the pore volume contributed by pores larger than 100.ANG..
9. A method for hydroprocessing hydrocarbonaceous feedstocks comprising:
contacting said feedstock with hydrogen under hydro-processing conditions in a first catalyst zone containing a first catalyst characterized by having no more than 5 weight percent Group VIII metal and producing a first effluent;
said first effluent with hydrogen under hydropro-cessing conditions in a second catalyst zone containing a second catalyst characterized by having no more than 4 weight percent Group VIII metal and no more than 7 weight percent Group VI metal and producing a second effluent; and contacting said second effluent with hydrogen under hydroprocessing conditions in a third catalyst zone con-taining a third catalyst characterized by having at least 2 weight percent Group VIII metal and at least 3 weight percent Group VI metal.
contacting said feedstock with hydrogen under hydro-processing conditions in a first catalyst zone containing a first catalyst characterized by having no more than 5 weight percent Group VIII metal and producing a first effluent;
said first effluent with hydrogen under hydropro-cessing conditions in a second catalyst zone containing a second catalyst characterized by having no more than 4 weight percent Group VIII metal and no more than 7 weight percent Group VI metal and producing a second effluent; and contacting said second effluent with hydrogen under hydroprocessing conditions in a third catalyst zone con-taining a third catalyst characterized by having at least 2 weight percent Group VIII metal and at least 3 weight percent Group VI metal.
10. The process of Claim 9 wherein said feedstock contains at least 20 ppm V + Ni + Fe and at least 1.0 weight percent sulfur.
11. The process of Claim 9 wherein said first catalyst and said second catalyst are characterized by having more than 10 percent pore volume contributed by pores larger than 1000.ANG..
12. The process of Claim 9 wherein said first catalyst and said second catalyst are supported on alumina.
13. The process of Claim 12 wherein said first catalyst is made by impregnating the alumina support with no more than 5 weight percent Group VIII metal and no more than 2 weight percent Group VI metal, and said second catalyst is made by impregnating said alumina support with at least 3 weight percent Group VIII metal and at least 2 weight percent Group VI metal.
14. The process of Claim 9 wherein said first catalyst has different Group VIII metals than said second catalyst.
15. The process of Claim 9 wherein said Group VIII
metals include nickel and cobalt, and said Group VI metals include molybdenum and tungsten.
metals include nickel and cobalt, and said Group VI metals include molybdenum and tungsten.
16. The process of Claim 9 wherein said first and said second catalysts have more than 50 percent of the pore volume contributed by pores larger than 100.ANG..
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43916382A | 1982-11-04 | 1982-11-04 | |
| US439,163 | 1982-11-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1228316A true CA1228316A (en) | 1987-10-20 |
Family
ID=23743567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000437430A Expired CA1228316A (en) | 1982-11-04 | 1983-09-23 | Treating residua with layers of differently impregnated hydroprocessing catalysts |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5998191A (en) |
| CA (1) | CA1228316A (en) |
| NL (1) | NL8303722A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300212A (en) * | 1992-10-22 | 1994-04-05 | Exxon Research & Engineering Co. | Hydroconversion process with slurry hydrotreating |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4916522A (en) * | 1972-06-08 | 1974-02-14 | ||
| JPS5398307A (en) * | 1977-02-08 | 1978-08-28 | Chiyoda Chem Eng & Constr Co Ltd | Hydrogenation of heavy oil |
| JPS5398308A (en) * | 1977-02-10 | 1978-08-28 | Chiyoda Chem Eng & Constr Co Ltd | Two-stage hydrogenation desulfurization of heavy oil |
| JPS5850636B2 (en) * | 1977-07-15 | 1983-11-11 | 千代田化工建設株式会社 | Desulfurization treatment method for heavy hydrocarbon oil |
| JPS5437105A (en) * | 1977-08-29 | 1979-03-19 | Chiyoda Chem Eng & Constr Co Ltd | Two-stage hydrogenation of heavy oil |
-
1983
- 1983-09-23 CA CA000437430A patent/CA1228316A/en not_active Expired
- 1983-10-28 NL NL8303722A patent/NL8303722A/en not_active Application Discontinuation
- 1983-11-02 JP JP20683483A patent/JPS5998191A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300212A (en) * | 1992-10-22 | 1994-04-05 | Exxon Research & Engineering Co. | Hydroconversion process with slurry hydrotreating |
Also Published As
| Publication number | Publication date |
|---|---|
| NL8303722A (en) | 1984-06-01 |
| JPS5998191A (en) | 1984-06-06 |
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